Use of copolymers on the basis of unsaturated acids or their derivatives as foam-protecting agent

ABSTRACT

The invention relates to the use of a copolymer or a mixture of copolymers as foam-protecting agents in detergent or cosmetic formulations, comprising at least one monomer (I) selected from the acids, diacids or unsaturated C3-C5 anhydrides; or at least one monomer (II) selected from ethylene oxide and propylene oxide; or at least one monomer (III) selected from the linear or branched C4-C8 hydrocarbons, comprising at least one ethenoid unsaturation; or at least one monomer (IV) of formula R1 —COO—R2, where R1 is a possibly substituted linear or branched C1-C3 hydrocarbon radical; R2 is a linear or branched C1-C4 hydrocarbon radical which is possibly substituted by an anionic radical or a hydroxyl group; and the monomer (IV) further comprises at least one ethenoid unsaturation.

This application is an application under 35 U.S.C. Section 371 ofInternational Application Number PCT/FR99/00091 filed on Jan. 19, 1999.

The present invention relates to copolymers in which one of the monomersis an unsaturated acid or diacid, or a derivative, as a foam protectorin detergent or cosmetic formulations.

The appearance of a large amount of long-lasting foam is a phenomenonwhich is very important to have in detergent or cosmetic formulations,more particularly those which are used by hand. The reason for this isthat it is clearly recognized that this foaming phenomenon issynonymous, for the user, with the efficacy of the cleaning undertaken.Consequently, even though this phenomenon does not really have anyeffect on the quality of the cleaning, a particular objective offormulators is to prepare formulations which give a large amount offoam.

However, the appearance and especially the durability of the foam arehighly dependent on the other compounds present in the bath, and mainlygreases. In other words, once the washing bath contains greasysubstances, the foam is more or less rapidly eliminated.

One aim of the present invention is to propose detergent and cosmeticformulations which generate large amounts of foam, and especially whichconserve this foam, in particular under unfavorable conditions, such asin the presence of greases, and possibly of divalent cations such ascalcium.

Thus, a subject of the present invention is the use, as a foam protectorin detergent or cosmetic formulations, of a copolymer or a mixture ofcopolymers comprising:

at least one monomer (I) chosen from C₃-C₅ unsaturated acids, diacids oranhydrides, or

at least one monomer (II) chosen from ethylene oxide and propyleneoxide, or

at least one monomer (III) chosen from linear or branched C₄-C₈hydrocarbons comprising at least one ethylenic unsaturation, or

at least one monomer (IV) of the following formula:

R ¹—COO—R ²,

in which:

R¹ represents a linear or branched, optionally substituted C₁-C₄hydrocarbon-based radical;

R² represents a linear or branched C₁-C₄ hydrocarbon-based radicaloptionally substituted with an anionic group which can be in the form ofan acid or of an alkali metal salt or ammonium salt of —N(R³)₃ ⁺ type,with R³, which may be identical or different, representing hydrogenatoms or C₁-C₄ hydrocarbon-based radicals, or optionally substitutedwith a hydroxyl group;

the monomer (IV) comprising at least one ethylenic unsaturation.

It should be noted that the term “foam protector”means a compound whichconserves this foam, at least partly, under unfavorable conditions, suchas in the presence of greases or of divalent cations. It should be notedthat the foamability of the polymer used as a foam protector in thepresent invention is not a criterion that is considered as trulyessential. However, the compound used should not excert a harmful effecton the ability of the foaming agents moreover present in theformulation.

The term “greases” refers more particularly to any liquid and/or solidhydrophobic hydrocarbon-based medium having, for example, a solubilityin water of less than 5 g/l, preferably less than 1 g/l.

This grease can be provided by the external medium and/or can be aconstituent of the detergent or cosmetic formulation. Thus, it can beeither a hydrophobic soiling or a hydrophobic active compound of saidformulation, for example.

Greases which may be mentioned as examples are:

aliphatic or aromatic hydrocarbons (alkanes (for example such ashexadecane), paraffins, mineral oils, liquid paraffins, kerosene,petrol, fuel, perhydrosqualane, squalene, etc.);

alkylmonoglycerides, alkyldiglycerides, triglycerides, such as the oilsextracted from plants and vegetation (palm oil, coconut oil, cotton seedoil, soybean oil, sunflower oil, olive oil, grape seed oil, sesame oil,ground nut oil, castor oil, hazlenut oil, etc.) or oils of animalorigin—tallow, fish oils), derivatives of these oils such ashydrogenated oils, and lanolin derivatives;

natural or non-natural essential oils, such as eucalyptus oil, lavenderoil, hybrid lavender oil, vetiver oil, lemon oil, orange oil, sandalwoodoil, rosemary oil, camomile oil, savory oil, nutmeg oil, cinnamon oil,bergamot oil, cade oil, geraniol oil, etc.,

fatty alcohols such as cetyl alcohol, stearyl alcohol or oleyl alcohol;

fatty esters such as isopropyl palmitate, 2-ethylhexyl cocoate, myristylmyristate, lactic acid esters, stearic acid esters, behenic acid esters,or isostearic acid esters;

polyorganosiloxane oils, gums or resins such as linear or cyclicpolydimethylsiloxanes, α,ω-hydroxylated polydimethylsiloxanes,α,ω-trimethylsilyl polydimethylsiloxanes, polyalkylmethylsiloxanes,polymethylphenylsiloxanes, polydiphenylsiloxanes, amino derivatives ofsilicones and silicone waxes;

organic soiling (sebum, etc.).

Thus, the use of these copolymers in detergent or cosmetic formulationsgives initial foaming properties that are at least as good as those ofconventional formulations. In addition, and this constitutes anoteworthy advantage of these copolymers, the use of these copolymers indetergent and cosmetic formulations makes it possible to conserve a foamvolume which is 10%, preferably 15% or even up to 30% greater than thatof formulations from which they are absent, and allows this in thepresence of greases possibly combined with divalent cations.

However, other aims and advantages of the present invention will emergemore clearly on reading the description and the examples which follow.

As has just been stated, the foam protector used in the presentinvention is a copolymer or a mixture of several copolymers comprisingat least one of the monomers (I) to (IV) mentioned previously.

More specifically, the copolymer or mixture of copolymers comprises atleast one monomer of at least two monomers of types (I) to (IV), of atleast two monomers of the type (IV) and optionally of at least onemonomer of type (I) to (III), or mixtures thereof.

It should be noted that the copolymer used as foam protector is moreparticularly soluble at the time of use of the formulation into which itis introduced, i.e. soluble in aqueous media.

More particularly, the copolymer is such that it is soluble in anaqueous solution of basic pH. Such conditions are conventional inparticular in the washing up of kitchenware and in the washing oflaundry.

In addition, the copolymer used according to the inventionadvantageously has both a hydrophilic part and a hydrophobic part. Thus,it lowers the interface tension between the aqueous solution and thegreases, which improves the dispersion of these greases in the aqueoussolution.

Generally, the copolymers used according to the invention have aweight-average molar mass of between 10³ and 10⁷ g/mol, moreparticularly between 10⁴ and 10⁶ g/mol and preferably between 10⁴ and5×10⁵ g/mol. According to an even more advantageous embodiment, thecopolymers have a weight-average molar mass of between 1.5×10⁴ and 5×10⁵g/mol. The molar mass is determined by steric exclusion chromatographyin aqueous phase. As an example of a method for measuring the molar massof the copolymers used in the context of the invention, a TSK-gelcolumn, with an eluent comprising water, 0.1 mol/l of NaO₃ and 200 ppmof NaN₃, was used. The detection of the molar mass is based on therefractive index, using polyethylene oxide as standard.

As more particularly regards the monomer (I), this monomer is chosenfrom C₃-C₅ unsaturated acids, diacids or anhydrides.

The most suitable representatives of these monomers are acrylic acid andmethacrylic acid. As regards the diacids and anhydrides, mention may bemade, inter alia, of maleic acid, fumaric acid, itaconic acid, maleicanhydride, furmaric anhydride and itaconic anhydride.

The monomer (II) is chosen from ethylene oxide and propylene oxide.

The monomer (III) is chosen from linear or branched hydrocarbonscomprising at least one C₄-C₈ ethylenic unsaturation. As examples ofmonomers of this type, mention may be made most particularly ofisobutylene and diisobutylene.

Finally, the monomer (IV) corresponds to the following formula:

R¹—COO—R²,

in which:

R¹ represents a linear or branched, optionally substituted C₁-C₄hydrocarbon-based radical;

R² represents a linear or branched C₁-C₄ hydrocarbon-based radical,optionally substituted with an anionic radical which can be in the formof an acid or of an alkali metal salt or ammonium salt of —N(R³)₃ ⁺type, with R³, which may be identical or different, representinghydrogen atoms or C₁-C₄ hydrocarbon-based radicals, or optionallysubstituted with a hydroxyl group;

the monomer (IV) comprising at least one ethyleneic unsaturation.

More particularly, said monomer (IV) is such that R¹ is derived fromacrylic acid, methacrylic acid or acetic acid.

It can also be envisaged to use a monomer (IV) whose radical R¹ issubstituted. It should be noted that the term “substituent” means apendant radical or a group which interrupts the hydrocarbon-based chain.Thus, suitable substituents which may be mentioned are the radicals —OH,—O—, —C(O)—, —C(O)—N— and —C(O)OR, with R representing a hydrogen atom,an alkali metal or a C₁-C₄ hydrocarbon-based radical, which ispreferably saturated.

The expression “anionic radical” is intended to denote sulfone, sulfate,phosphate, phosphonate and carboxylic radicals. A sulfone monomer ispreferably used.

According to one specific embodiment of the invention, the monomer (IV)comprises at least one ethylenic unsaturation. If there is only oneunsaturation, it can be either on the radical R¹ or on the radical R².If there are several unsaturations, they can be on the radical R¹, onthe radical R² or on both the radicals R¹ and R².

A monomer comprising only one ethylenic unsaturation is preferably used.

Consequently, if the monomer (IV) is derived from an acid bearing anunsaturation, then the radical R² does not bear any ethylenicunsaturation. On the other hand, in the opposite case, the radical R²comprises the ethylenic unsaturation.

A first embodiment of the invention consists of the use of a copolymercomprising at least one monomer (I) and at least one monomer (III).

This copolymer preferably comprises maleic acid or maleic anhydride asmonomer (I) and isobutylene or diisobutylene as monomer (III).

The copolymer can be in the acid form or in the form of an alkali metalsalt or ammonium salt of —N(R³)₃ ⁺ type, with R³, which may be identicalor different, representing hydrogen atoms or C₁-C₄ hydrocarbon-basedradicals. Preferably, the copolymer is in the form of sodium salts.

The monomers are distributed alternately in the molecule.

The proportion of the monomer (I) relative to the monomer (III) is50/50.

These copolymers are well-known compounds and are sold in particularunder the name Geropon® T 36 (Rhodia Chimie).

A second embodiment of the invention consists of the use of a copolymercomprising at least one monomer (I) and at least one monomer (II).

This copolymer more particularly comprises a polymer chain consisting ofthe monomer(s) (II) onto which are grafted polymer chains derived fromthe monomer(s) (I).

According to one particularly advantageous variant of the invention,said copolymer comprises acrylic acid as monomer (I), and ethylene oxideor an ethylene oxide/propylene oxide mixture as monomer (II). In thecase of an ethylene oxide/propylene oxide mixture, a chain containing anordered distribution, corresponding to a dibloc of the twoabovementioned monomers, is preferably used.

The copolymer according to this variant has a weight proportion ofmonomer (II) ranging from 1 to 50% relative to the weight of thecopolymer. Preferably, it is between 1 and 30% relative to the weight ofthe copolymer.

These copolymers can be obtained by any means known to those skilled inthe art.

For example, they are obtained by carrying out a polymerization, in asuitable solvent, of the monomer (I) and of the polymer chain consistingeither of ethylene oxide alone or of an ethylene oxide/propylene oxidemixture, in the presence of an initiator for generating free radicals.The reaction is generally carried out using water or an alcohol/watermixture. In addition, the polymerization reaction is carried out in thepresence of a base, such that, if it is present, the monomer (I) ispartially neutralized.

According to a third embodiment of the invention, the copolymer used asfoam protector optionally comprises at least one monomer (I) and atleast one monomer (IV).

The monomer (IV) can be chosen more particularly from the followingmonomers: vinyl acetate; alkyl acrylate; alkyl methacrylate; alkylmethacrylate or acrylate bearing, as anionic group, a sulfonated(sulfoalkyl) group, in the form of an acid or of an alkali metal salt orammonium salt of —N(R³)₃ ⁺ type; hydroxyalkyl acrylate or methacrylate;monomers in which the alkyl radical corresponds to methyl, ethyl, propyland propyl isomer, butyl and butyl isomer radicals.

As regards the sulfonated monomers, monomers in salt form are moreparticularly used, preferably in the form of an alkali metal salt.Examples of monomers of sulfoalkyl type which may be mentioned aresodium sulfoethyl acrylate and sodium sulfoethyl methacrylate.

As regards the monomer comprising a hydroxyalkyl group, 2-hydroxyethylacrylate and 2-hydroxyethyl methacrylate are advantageous examples.

It should be noted that the copolymer can comprise one or more monomers(IV), with or without monomer (I).

A first type of particularly advantageous copolymer has the followingcomposition:

monomer (I) 0-50% by weight monomer (IV): vinyl acetate 0-92% by weightC₁-C₄ alkyl (preferably 0-50% by weight butyl) (meth)acrylate sodiumC₁-C₄ sulfoalkyl 0-10% by weight (preferably sulfoethyl) (meth)acrylate

the sum of each of the monomers used being equal to 100% relative to theweight of the copolymer.

This copolymer more particularly comprises 1-15% of monomer (I); 50-85%of vinyl acetate; 5-20% of alkyl acrylate or methacrylate; 0.5-5% ofsodium sulfoalkyl acrylate or methacrylate; the sum of each of themonomers used being equal to 100% relative to the weight of thecopolymer.

When the copolymer comprises at least one monomer (I), this monomer ischosen more particularly from acrylic acid and methacrylic acid.

A second type of very advantageous copolymer consists in using a monomer(I), and preferably (meth)acrylic acid, and one at least one monomer(IV) comprising a hydroxyl substituent, which is preferably a2-hydroxyalkyl acrylate or 2-hydroxyalkyl methacrylate, in which thealkyl radical is C₁-C₄, preferably C₂. The proportion of monomer (I)relative to the monomer (IV) is between 0.1 and 90% by weight relativeto the weight of the copolymer.

The proportion of monomer (I) in this second type of copolymer is moreparticularly 0.1-50% by weight relative to the weight of the copolymer,preferably 20-60% by weight.

The copolymers used in this third embodiment of the invention arepreferably copolymers with a random distribution of the various monomersmentioned above.

These copolymers can be obtained in this case also by implementing meansthat are conventional for those skilled in the art.

Thus, the polymerization can take place in solution or in emulsion, byintroducing the various monomers in the presence of a compound forgenerating free radicals. The reaction is generally carried out usingwater or an alcohol/water mixture. It is possible to carry out thepolymerization reaction in solution or in emulsion, in which case it isnecessary to use a surfactant. Furthermore, common compounds can beused, if necessary, such as buffers, bases to neutralize the acids, ifsuch monomers are present, and transfer agents (for limiting the growthof the chains).

The foam protector is thus used in detergent or cosmetic formulations,and it represents more particularly 0.05 to 10% by weight of theformulation, more particularly between 0.05 and 2% by weight. The amountof foam protector advantageously represents 0.5 to 2% by weight of theformulation.

The detergent formulations in which the foam protector can be used aremore especially household detergent formulations intended for washing upkitchenware by hand or washing laundry by hand.

In the field of household detergency, the present invention is directedmore particularly toward liquid compositions for washing up kitchenwareby hand.

Said compositions, besides the foam protector according to theinvention, can contain from about 0.5 to about 40% by weight of anionicsurfactants, from about 0.5 to about 10% by weight of nonionicsurfactants and 0 to 20% by weight of zwitterionic or amphotericsurfactants.

ANIONIC SURFACTANTS

alkyl sulfates of formula ROSO₃M, in which R represents a C₁₀-C₂₄,preferably C₁₂-C₂₀ and most particularly C₁₂-C₁₈, alkyl radical orhydroxyalkyl radical, M representing a hydrogen atom or a cation of thesame definition as above, as well as the ethoxylenated (EO) and/orpropoxylenated (PO) derivatives thereof, containing on average from 0.5to 6 and preferably from 0.5 to 3 EO and/or PO units;

alkyl ether sulfates;

alkylglycoside sulfates;

alkylamide sulfates of formula RCONHR′OSO₃M in which R represents aC₂-C₂₂, preferably C₆-C₂₀, alkyl radical, R′ represents a C₂-C₃ alkylradical, M representing a hydrogen atom or a cation of the samedefinition as above, as well as the ethoxylenated (EO) and/orpropoxylenated (PO) derivatives thereof, containing on average 0.5 to 60EO and/or PO units;

C₉-C₂₀ alkylaryl sulfonates, primary or secondary C₈-C₂₂ alkylsulfonates, alkylglyceryl sulfonates, the sulfonated polycarboxylicacids described in GB-1 082 179, sulfonated fatty acid derivatives;paraffin sulfonates;

alkyl ester sulfonates of formula R—CH(SO₃M)—COOR′, in which Rrepresents a C₈-C₂₀, preferably C₁₀-C₁₆, alkyl radical, R′ represents aC₁-C₆, preferably C₁-C₃, alkyl radical and M represents an alkali metal(sodium, potassium or lithium) cation, substituted or unsubstitutedammonium (methyl-, dimethyl-, trimethyl- or tetramethylammonium,dimethylpiperidinium, etc.) or an alkanolamine derivative(monoethanolamine, diethanolamine, triethanolamine, etc.). Mention maybe made most particularly of methyl ester sulfonates in which theradical R is C₁₄-C₁₆;

alkyl phosphates;

polyethoxycarboxylates; the cation being an alkali metal (sodium,potassium or lithium), a substituted or unsubstituted ammonium residue(methyl-, dimethyl-, trimethyl- or tetramethylammonium,dimethylpiperidinium, etc.) or an alkanolamine derivative(monoethanolamine, diethanolamine, triethanolamine, etc.);

saturated or unsaturated C₈-C₂₀, preferably C₁₂-C₁₆, fatty acid salts,N-acyl N-alkyltaurates, alkyl isethionates, alkyl succinamates, alkylsulfosuccinates, sulfosuccinate monoesters or diesters and N-acylsarcosinates.

NONIONIC SURFACTANTS

polyoxyalkylenated (polyoxyethylenated, polyoxypropylenated orpolyoxybutylenated) alkyl phenols in which the alkyl substituent isC₆-C₁₂ and containing from 5 to 25 oxyalkylene units; examples which maybe mentioned are the products Triton X-45, X-114, X-100 or X-102;

glucosamide, glucamide;

glycerolamides derived from N-alkylamines (U.S. Pat. No. 5,223,179 andFR 1 585 966);

polyoxyalkylenated C₈-C₂₂ aliphatic alcohols containing from 1 to 25oxyalkylene (oxyethylene or oxypropylene) units; examples which may bementioned are the products Tergitol 15-S-9, Tergitol 24-L-6 NMW, Neodol45-9, Neodol 23-65, Neodol 45-7, Neodol 45-4 and Kyro EOB;

products resulting from the condensation of ethylene oxide with ahydrophobic compound resulting from the condensation of propylene oxidewith propylene glycol, such as the Pluronic products;

products resulting from the condensation of ethylene oxide the compoundresulting from the condensation of propylene oxide with ethylenediamine, such as the Tetronic products;

amine oxides such as (C₁₀-C₁₈)alkyldimethylamine oxides and(C₈-C₂₂)alkoxyethyldihydroxyethylamine oxides;

the alkylpolyglycosides described in U.S. Pat. No. 4,565,647;

oxyalkylenated derivatives of fatty alcohols, such as the Plantaren®products;

C₈-C₂₀ fatty acid amides;

ethoxylated fatty acids;

ethoxylated fatty amides;

ethoxylated amines.

AMPHOTERIC AND ZWITTERIONIC SURFACTANTS

alkyldimethylbetaines, alkylamidopropyldimethylbetaines andalkyltrimethylsulfobetaines;

alkyl amphoacetates or alkyl amphodiacetates, such as the products ofthe Miranol® range;

the products of condensation of fatty acids with proteins or proteinhydrolysates;

amphoteric alkylpolyamine derivatives such as Amphionic XL®, Ampholac7T/X® and Ampholac 7C/X®.

The formulations can contain other additives, such as:

VISCOSITY MODIFIERS, such as:

cellulose derivatives such as carboxymethylcellulose orhydroxyethylcellulose;

guar derivatives such as hydroxypropylguar, carboxymethylguar orcarboxymethylhydroxypropylguar.

HYDROTROPIC AGENTS:

C₂-C₈ short alcohols, in particular ethanol, but also methanol, propanoland isopropanol;

diols and glycols such as propanediol, ethylene glycol, diethyleneglycol or dipropylene glycol. It should be noted that the amphotericsurfactants can also act as hydrotropic agents, as can toluenesulfonate,xylenesulfonate and urea.

MOISTURIZERS OR SKIN PROTECTORS, such as:

glycerol;

urea;

proteins or protein hydrolysates;

cationic polymers such as cationic guar derivatives (Jaguar C13S®,Jaguar C162® or Hicare 1000®.

OTHER ADDITIVES such as:

bactericides or disinfectants such as triclosan;

buffers;

fragrances;

pigments, dyes;

preserving agents.

As more particularly regards the formulations intended for washinglaundry by hand (liquid or solid formulations), these formulations cancomprise, besides the foam protector according to the invention, thefollowing elements:

SURFACTANTS, in an amount corresponding to about 3-40% by weightrelative to the detergent composition. The lists of surfactants whichwere given for the household detergency formulations remain valid andwill not be repeated here. Reference may thus be made thereto.

BUILDERS, in an amount corresponding to about 5-50%, preferably to about5-30%, by weight for the liquid detergent formulations, or to about10-80%, preferably 15-50%, by weight for the powdered detergentformulations, such as:

Inorganic Builders:

polyphosphates (tripolyphosphates, pyrophosphates, orthophosphates orhexametaphosphates) of alkali metals, of ammonium or of alkanolamines;

tetraborates;

silicates, in particular those with an SiO₂/Na₂O ratio from about 1.6/1to 3.2/1 and the lamellar silicates described in U.S. Pat. No.4,664,839;

alkali metal or alkaline-earth metal carbonates (bicarbonates,sesquicarbonates);

cogranulates of alkali metal silicate hydrates and of alkali metal(sodium or potassium)-carbonates which are rich in silicon atoms, in Q2or Q3 form, described in EP 488 868;

crystalline or amorphous alkali metal (sodium or potassium) or ammoniumaluminosilicates, such as zeolites A, P, X, etc.; zeolite A withparticle sizes of about 0.1-10 micrometers is preferred.

Organic Builders:

water-soluble polyphosphonates (ethane 1-hydroxy-1,1-diphosphonates,methylene diphosphonate salts, etc.);

water-soluble salts of carboxylic polymers or copolymers orwater-soluble salts thereof, such as:

polycarboxylate ethers (oxydisuccinic acid and its salts, tartaric acidand its salts, succinic acid and its salts, or co-products thereof);

hydroxypolycarboxylate ethers;

citric acid and its salts, mellitic acid and succinic acid, and saltsthereof;

polyacetic acid salts (ethylenediaminetetraacetates, nitrilotriacetates,N-(2-hydroxyethyl)nitrilodiacetates);

C₅-C₂₀ alkylsuccinic acids and salts thereof (2-dodecenylsuccinates,lauryl succinates);

polycarboxylic acetal esters;

polyaspartic acid, polyglutamic acid and salts thereof;

polyimides derived from the polycondensation of aspartic acid and/orglutamic acid;

polycarboxymethyl derivatives of glutamic acid or of other amino acids.

ANTI-SOILING AGENTS, in an amount of about 0.01-10%, preferably about0.1-5% and most particularly of about 0.2-3% by weight, such as:

cellulose derivatives such as cellulose hydroxy ethers, methylcellulose,ethylcellulose, hydroxypropylmethylcellulose orhydroxybutylmethylcellulose;

polyvinyl ethers grafted onto polyalkylenated trunks, such as polyvinylacetates grafted onto polyoxyethylene trunks (EP 219 048);

polyvinyl alcohols;

polyester copolymers based on ethylene terephthalate and/or propyleneterephthalate and polyoxyethylene terephthalate units, with an ethyleneterephthalate and/or propylene terephthalate (number ofunits)/polyoxyethylene terephthalate (number of units) molar ratio fromabout 1/10 to about 10/1, preferably from about 1/1 to about 9/1, thepolyoxyethylene terephthalates containing polyoxyethylene units with amolecular weight from about 300 to about 5000, preferably from about 600to about 5000 (U.S. Pat. Nos. 3,959,230, 3,893,929, 4,116,896,4,702,857, 477,066);

sulfonated polyester oligomers obtained by sulfonation of an oligomerderived from ethoxylated allylic alcohol, from dimethyl terephthalateand from 1,2-propylene diol, containing from 1 to 4 sulfonated groups(U.S. Pat. No. 4,968,451);

polyester copolymers based on propylene terephthalate andpolyoxyethylene terephthalate units and ending with ethyl or methylunits (U.S. Pat. No. 4,711,730) or polyester oligomers ending withalkylpolyethoxy groups (U.S. Pat. No. 4,702,857) or sulfopolyethoxy(U.S. Pat. No. 4,721,580) or sulfoaroyl (U.S. Pat. No. 4,877,896)anionic groups;

polyester-polyurethanes obtained by reacting polyesters with anumber-average molecular mass of 300-4000 obtained from adipic acidand/or terephthalic acid and/or sulfoisophthalic acid and from a diolwith a mass of less than 300, with a prepolymer containing isocyanateend groups obtained from a polyoxyethylene glycol with a molecular massof 600-4000 and from a diisocyanate (FR 2 334 698).

ANTI-REDEPOSITION AGENTS, more particularly in formulations intended forwashing laundry, in an amount of about 0.01-10% by weight for a powdereddetergent composition, and of about 0.01-5% by weight for a liquiddetergent composition, such as:

ethoxylated monoamines or polyamines, and ethoxylated amine polymers(U.S. Pat. No. 4,597,898, EP 11984);

carboxymethylcellulose;

sulfonated polyester oligomers obtained by condensation of isophthalicacid, dimethyl sulfosuccinate and diethylene glycol (FR 2 236 926);

polyvinylpyrrolidones.

CHELATING AGENTS for chelating calcium, magnesium and iron, in an amountof about 0.1-10%, preferably of about 0.1-3%, by weight, such as;

aminocarboxylates such as ethylenediaminetetraacetates, hydroxyethylethylenediaminetriacetates and nitrilotriacetates;

aminophosphonates such as nitrilotris(methylene phosphonates);

polyfunctional aromatic compounds such as dihydroxydisulfobenzenes.

POLYMERIC DISPERSANTS, in an amount of about 0.1-7% by weight, tocontrol the calcium and magnesium hardness, such as:

water-soluble polycarboxylic acid salts with a molecular mass from about2000 to about 100,000, obtained by polymerization or copolymerization ofethylenically unsaturated carboxylic acids such as acrylic acid, maleicacid or anhydride, fumaric acid, itaconic acid, aconitic acid, mesaconicacid, citraconic acid or methylenemalonic acid, and most particularlypolyacrylates with a molecular mass from about 2000 to about 10,000(U.S. Pat. No. 3,308,067), copolymers of acrylic acid and of maleicanhydride with a molecular mass from about 5000 to about 75,000 (EP66915);

FLUORESCERS, in an amount of about 0.05-1.2% by weight, such as:

stilbene, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles,methinecyanin, thiophene, etc. derivatives (“The production andapplication of fluorescent brightening agents”—M. Zahradnik, publishedby John Wiley & Sons, New York-1982-).

SOFTENERS, in an amount of about 0.5-10% by weight, such as clays.

ENZYMES in an amount which can be up to 5 mg by weight, preferably about0.05-3 mg, of active enzyme/g of detergent composition, such as:

proteases, amylases, lipases, cellulases and peroxidases (U.S. Pat. Nos.3,553,139, 4,101,457, 4,507,219, 4,261,868).

OTHER ADDITIVES such as:

alcohols (methanol, ethanol, propanol, isopropanol, propanediol,ethylene glycol, glycerol);

buffers;

fragrances;

pigments.

The foam protector according to the invention can likewise form part ofthe composition of cosmetic formulations such as, inter alia, hair orbody shampoo formulations, body or facial cleansing gels, liquid soapsand bubble bath compositions.

Besides the agent according to the invention, said formulations cancomprise at least one of the following elements:

SURFACTANTS, of anionic type, where appropriate combined with nonionic,zwitterionic and amphbteric surfactants, in an amount ranging from 0.05to 20% of the weight of the preparation. In this case also, referencemay be made to the lists of surfactants given previously.

WETTING AGENTS, such as:

glycerol, sorbitol;

urea;

collagen, gelatin;

aloe vera;

hyaluronic acid.

EMOLLIENTS, such as:

alkylmonoglycerides, alkyldiglycerides and triglycerides, such as oilsextracted from plants and vegetation (palm oil, coconut oil, cotton seedoil, soybean oil, sunflower oil, olive oil, grape seed oil, sesame oil,groundnut oil, castor oil, etc.) or oils of animal origin (tallow, fishoils, etc.), derivatives of these oils, such as hydrogenated oils,lanolin derivatives, mineral oils or liquid paraffins, perhydrosqualane,squalene;

diols such as 1,2-propanediol, 1,3-butanediol, cetyl alcohol, stearylalcohol, oleyl alcohol, polyethylene glycols or polypropylene glycols;

fatty esters such as isopropyl palmitate, 2-ethylhexyl cocoate, myristylmyristate or lactic acid esters,

stearic acid, behenic acid, isostearic acid,

silicone oils combining cyclic polydimethylsiloxanes, α,ω-hydroxylatedpolydimethylsiloxanes, α,ω-trimethylsilyl polydimethylsiloxanes,polyorganosiloxanes such as polyalkylmethylsiloxanes,polymethylphenylsiloxanes, polydiphenylsiloxanes, aminosiliconederivatives, silicone waxes, copolyether silicones (such as the oilSilbione 70646® or DC 190®) or mixed silicone derivatives such aspolyalkylmethylsiloxane-silicone copolyether mixed copolymers.

MINERAL PARTICLES OR SUNSCREENS, such as:

calcium carbonate,

inorganic oxides in powder form or in colloidal form (particles of lessthan or about one micrometer in size, occasionally a few tens ofnanometers) such as titanium dioxide, silica, aluminum salts, kaolin,talc, clays and derivatives thereof, etc.

PRESERVING AGENTS, in an amount from about 0.01 to about 3% by weight,such as:

methyl, ethyl, propyl and butyl esters of p-hydroxybenzoic acid,

sodium benzoate, Germaben®.

As alternatives to these chemical agents, agents which modify the wateractivity and which greatly increase the osmotic pressure canoccasionally be used, such as carbohydrates or salts.

VISCOSITY MODIFIERS/GELLING AGENTS, such as:

Carbopol® crosslinked polyacrylates;

cellulose derivatives such as hydroxypropylcellulose,carboxymethylcellulose;

guars and derivatives thereof, carob, tara gum or cassia gum;

xanthan gum;

alginates, carrageenans;

chitin derivatives such as chitosan.

The foam protector according to the invention can similarly be used incleansing bar formulations known as toiletry soaps or general purposesoaps.

Conventional cleansing bar compositions generally comprise fatty acidsalts used in combination with the agent according to the invention, butalso surfactants other than fatty acid salts or the fatty acidsthemselves, which are mentioned previously.

These compositions can even contain no fatty acid or fatty acid salt,and in this case their formulations are based on other surfactants suchas, for example, sodium C₈-C₂₂ alkyl isethionates or sodium C₈-C₂₂ alkylsulfates.

AGENTS FOR REDUCING SKIN IRRITATION/MOISTURIZERS

alkali metal salts or isethionates;

carbohydrates (glycerol or sorbitol for example);

polyethylene glycols or polypropylene glycol;

alkoxylated sugar derivatives or derivatives thereof (for example methylglucose);

water-soluble or water-dispersible polymers such as collagen or certainnon-allgergenic derivatives of animal or plant proteins (for examplewheat protein hydrolysates);

natural hydrocolloids (guar gum, carob gum, tara gum, etc.) orhydrocolloids derived from fermentation processes, such as xanthan gum,and derivatives of these polycarbohydrates such as modified celluloses(for example hydroxyethylcellulose, carboxymethylcellulose or cationiccelluloses such as the products Polymer JR®), guar or carob derivativessuch as cationic derivatives thereof (Jaguar C13S®, Jaguar C162®) ornonionic derivatives (for example hydroxypropylguar), anionicderivatives (carboxymethylguar) or nonionic/anionic mixed derivativessuch as carboxyhydroxypropylguars or nonionic/cationic mixedderivatives. Synthetic polymers such as polyacrylates or syntheticcationic polymers, known under the CTFA generic name “Polyquaternium”,for example the polymers Mirapol A15® or Mirapol 550®, can also be addedalternatively or in combination.

SEQUESTERING AGENTS for sequestering calcium, such as citrate ions.

EMOLLIENTS such as silicones or oils or fatty substances used in thisrespect in the cosmetics industry (mineral oils, fatty acid esters,triglycerides, silicones, etc.).

ADDITIVES

fragrances,

dyes and/or opacifiers such as pigments (titanium oxide particles);

bactericides or fungicides.

In a cleansing bar whose formulation consists mainly of soaps ofmonocarboxylic fatty acids (sodium, potassium, mono-, di- ortriethanolammonium salts), the fatty acid contents of the soaps aregenerally more than 25% by weight of the formulation, generally from 30to 95% by weight.

In a cleansing bar whose formulation is based on main constituents otherthan fatty acid soaps, from 0 to 50% by weight, preferably from 1 to 40%by weight, of these fatty acid soaps are found in the formulation.

These cleansing bar compositions can also contain from 0 to 95%,preferably from 0 to 60%, of surfactants other than soaps, in particularC₈-C₂₂ alkyl or alkenyl isethionates, as well as alkyl ether sulfates,alkylbetaines, alkylamidopropylbetaines, alkylampho-acetates,-diacetates, -propionates or -dipropionates used to reduce theirritation which may be caused by the other surfactants, mainly theanionic surfactants.

From 1 to 15% of C₈-C₂₂ free fatty acids can also be introduced into thesoap compositions as overfatting agents or to modify the appearance andthe creamy nature of the foam during washing.

Waxes such as paraffin waxes, natural waxes such as beeswax orozokerites or silicone waxes can also be found in these compositions.These waxes are advantageously used to improve the appearance, behavior,processibility and conservation on storage of the cleansing bars.

The shampoos, and more generally the detergent compositions forpersonal-hygiene use, can contain, besides the foam protector accordingto the invention, the common additives present in formulations of thistype.

Mention May be Made in Particular of:

SURFACTANTS such as those indicated previously, in an amount rangingfrom 5 to 25%.

CONDITIONERS such as:

synthetic cationic polymers such as Mirapol AD1® or Mirapol A550®,natural cationic polymers such as cationic guar derivatives (JaguarC135®, Jaguar C162®) or cationic cellulose derivatives (Polymer JR400®);

polyorganosiloxanes used in their native form or dissolved in a commonsolvent therefor (silicone oils of low mass, highly branched liquidparaffins, fatty esters such as, for example, isopropyl palmitate,etc.).

ANTIDANDRUFF AGENTS, such as:

pyridinethiones, more especially zinc pyridinethione,

selenium-based compounds such as selenium sulfide or Octopyrox®.

AGENTS FOR MODIFYING THE APPEARANCE OR THE VISCOSITY, such as:

pearlescent compounds based on polyethylene glycol stearate;

the Carbopol® products,

hydrocolloids and derivatives thereof, such as guar or modified guars,carob, xanthan gum and cellulose derivatives (hydroxyethylcellulose,carboxymethylcellulose).

OTHER ADDITIVES, such as:

anti-parasitic (anti-louse) agents, such as Lindane or variouspyrethrins;

dyes, pigments;

fragrances.

Concrete but nonlimiting examples of the invention will now be given.

EXAMPLE 1

The subject of this example is the preparation of a copolymer based onacrylic acid and on ethylene oxide.

10 g of sodium hydroxide are dissolved in 680 g of water, at roomtemperature, in a 2 liter glass reactor equipped with a jacket and astirrer (190 rpm). The temperature is then increased to 65° C.

An initiator solution comprising 0.105 g of ammonium persulfate and 30 gof water is prepared.

Separately, a solution comprising 30 g of water and 70 g of acrylic acidand a solution comprising 10 g of sodium hydroxide and 30 g of water aremixed.

14 g of polyethylene oxide (100,000 g/mol) are dissolved in the reactor.Next, the solution comprising the acrylic acid and the initiatorsolution are introduced continuously. The operation is carried out over300 minutes, while maintaining a constant rate of introduction andkeeping the temperature at 65° C.

Once the introduction is complete, the reaction mixture is left stirringfor 120 minutes at 65° C.

The mixture is finally cooled to room temperature.

A copolymer is obtained in which the polyoxyethylenated chain bearsgrafts of polyacrylic acid type.

The pH is 4.8.

The solids content is 12%.

EXAMPLE 2

The subject of this example is the preparation of a copolymer based onacrylic acid and on ethylene oxide/propylene oxide.

10 g of sodium hydroxide are dissolved in 630 g of water, at roomtemperature, in a 2 liter glass reactor equipped with a jacket and astirrer (190 rpm). The temperature is then increased to 65° C.

An initiator solution comprising 0.46 g of ammonium persulfate and 10 gof water is prepared.

Separately, a solution comprising 28 g of water and 92 g of acrylic acidis prepared.

18.4 g of a polyethylene oxide/polypropylene oxide dibloc copolymer(6500 g/mol, 50% ethylene oxide) and 180 g of ethanol are introducedinto the reactor.

Next, the initiator solution is added once the dibloc copolymer hasdissolved.

The solution comprising the acrylic acid is then added continuously,over a period of 120 minutes, while maintaining a constant rate ofintroduction and keeping the temperature at 65° C.

Once the introduction is complete, the reaction mixture is left stirringfor 120 minutes at 65° C.

The mixture is finally cooled to room temperature.

A copolymer is obtained whose polyoxyethylenated/polyoxypropylenatedchain bears grafts of polyacrylic acid type.

The pH is 4.8.

The solids content is 12%.

EXAMPLE 3

This example illustrates the preparation of a copolymer comprising vinylacetate, acrylic acid, butyl acrylate and sodium sulfoethyl methacrylateas monomers.

A mixture comprising 150.6 g of water, 1.6 g of sodium lauryl sulfate,7.21 g of an aqueous solution of 44.35% sodium sulfoethyl methacrylateand 1.6 g of sodium acetate is introduced into a 2 liter glass reactorequipped with a jacket and a stirrer (190 rpm), and the reactor isbrought to 70° C.

An initiator solution comprising 1.6 g of ammonium persulfate and 6 g ofwater is prepared and is introduced into the reactor at t=to.

A mixture comprising 150 g of water, 246.4 g of vinyl acetate, 51.2 g ofbutyl acrylate, 22.4 g of acrylic acid and 1.6 g of sodium laurylsulfate is emulsified. The emulsion is then added to the reactor over aperiod of 5 hours starting from to.

The following are then added:

a solution of 2.176 g of sodium sulfoxide and 1.6 g of sodiumbicarbonate in 48 g of water, over 7 hours starting from to;

a solution of 1.83 g of tert-butyl hydroperoxide (70%) and 40 g ofwater, over 7 hours starting from to.

The temperature is then increased to 80° C. and maintained for one hourbefore cooling.

A random copolymer is obtained.

EXAMPLE 4

This example illustrates the preparation of a copolymer comprisingacrylic acid and 2-hydroxyethyl methacrylate.

10 g of sodium hydroxide dissolved in 252 g of water are introduced, atroom temperature, into a 2 liter glass reactor equipped with a jacketand a stirrer (190 rpm).

The temperature is then increased to 65° C.

A mixture of 408 g of water, 55 g of 2-hydroxyethyl methacrylate, 55 gof acrylic acid and 0.22 g of methyl mercaptopropionate is prepared.

A solution comprising 1.1 g of ammonium persulfate is introduced intothe reactor. The above mixture is then added continuously over a periodof 120 minutes, at a temperature of 65° C.

Once the introduction is complete, the reaction mixture is left stirringfor 120 minutes at 65° C.

The mixture is finally cooled to [lacuna] temperature.

A copolymer with a random distribution of monomers is obtained.

The pH is 7.2.

The solids content is 15.3%.

EXAMPLE 5

The subject of this example is the use of each of the copolymersobtained above in a detergent formulation, in the presence of grease.

The detergent formulation used comprises:

21% by dry weight of sodium lauryl ether sulfate (Empicol ESB/3M sold byAlbright & Wilson);

3% by dry weight of ethoxylated alcohol containing on average 6oxyethylene units (Rhodasurf IDO60 sold by Rhodia Chimie);

3% by dry weight of cocoamidopropylbetaine (Dehyton K sold by Henkel);

qs 100% by weight of water.

The pH was adjusted to 7.

The copolymers obtained previously were tested separately with theformulation described above, the copolymer content being 2% by weightrelative to that of the formulation, and the whole being diluted to 1%.

The test consists in carrying out the following:

250 ml of the formulation described previously are introduced into a 500ml flask and 7 ml of grease (50/50 by weight mixture of sunflower oiland margarine) are added.

The flask is stoppered and is then subjected to series of upturning, atan upturning rate of 60 turns per minute.

The results show that the volume of foam maintained in the presence ofthe grease used remains about 15% higher in the case of formulationscomprising the copolymer according to the invention, than that of aformulation not containing it.

What is claimed is:
 1. A method of conserving foams generated be a foamforming formulation, comprising the step of adding to said formulation,an effective foam conserving amount of a copolymer or a mixture ofcopolymers comprising: at least one monomer (I) which is a C₃-C₅unsaturated acid, a diacid or an anhydride, at least one monomer (II)which is ethylene oxide or propylene oxide, at least one monomer (III)which is a linear or branched C₄-C₈ hydrocarbon comprising at least oneethylenic unsaturation, at least one monomer (IV) which is vinylacetate; alkyl acrklate; alkyl methacrylate; alkyl methacrylate oracrylate bearing a sulfoalkyl group, in the form of an acid or of analkali metal salt or ammonium salt of formula: —N(R³)₃ ⁺, wherein R³,which are identical or different, represent a hydrogen atom or C₁-C₄hydrocarbon radical, optionally substituted with a hydroxyl group;hydroxyalkyl acrylate; or hydroxyalkyl methacrylate, said alkyl radicalbeing methyl, ethyl, propyl, prropyl isomer, butyl, or butyl isomer,saidcopolmer comprising at least one monomer (I) and at least one monomer(IV), and having the following composition: 1-15% of monomer (I); 50-85%of vinyl acetate; 5-20% of alkyl acrylate or methacrylate; 0.5-5% ofsodium sulfoalkyl acrylate or methacrylate; and the sum of each of themonomers used being equal to 100% relative to the weight of thecopolymer.
 2. A method according to claim 1, wherein the monomer (I) isacrylic acid or methacrylic acid.
 3. A method according to claim 1,wherein the monomer (IV) is 2-hydroxyethyl acrylate, or 2-hydroxyethylmethacrylate and the monomer (I) is acrylic acid, or methacrylic acid.4. A method according to claim 1, wherein the proportion of monomer (I)relative to the monomer (IV) is between 0.1 and 90% by weight relativeto the weight of the copolymer.
 5. A method according to claim 1,wherein the amount of the copolymer represents 0.05 to 10% by weight ofthe formulation.
 6. A method according to claim 5, wherein the amount offoam protector copolymer represents 0.05 and 2% by weight.
 7. A methodaccording to claim 1, wherein the formulation is a detergent formulationfor washing up kitchenware by hand or washing laundry by hand.